REVIEWS

ªSynthetic Metalsº: A Novel Role for Organic Polymers (Nobel Lecture)**

Alan G. MacDiarmid*

Since the initial discovery in 1977, that
polyacetylene (CH)x , now commonly
known as the prototype conducting
polymer, could be p- or n-doped either
chemically or electrochemically to the
metallic state, the development of the
field of conducting polymers has con-
tinued to accelerate at an unexpectedly
rapid rate and a variety of other
conducting polymers and their deriva-
tives have been discovered. Other
types of doping are also possible, such
as ªphoto-dopingº and ªcharge-injec-
tion dopingº in which no counter
dopant ion is involved. One exciting
challenge is the development of low-
cost disposable plastic/paper electronic
devices. Conventional inorganic con-
ductors, such as metals, and semicon-
ductors, such as silicon, commonly
require multiple etching and litho-
graphic steps in fabricating them for
use in electronic devices. The number
of processing and etching steps in-
volved limits the minimum price. On
the other hand, conducting polymers
combine many advantages of plastics,
for example, flexibility and processing
from solution, with the additional ad-
vantage of conductivity in the metallic
or semiconducting regimes; however,
the lack of simple methods to obtain
inexpensive conductive polymer
shapes/patterns limit many applica-
tions. Herein is described a novel,
simple, and cheap method to prepare
patterns of conducting polymers by a
process which we term, ªLine Pattern-
ingº.
Keywords: conducting materials ´
liquid crystals ´ nano-electronics ´
Nobel lecture ´ polymers

Introduction increased by several orders of magnitude from the semi-

conductor regime are generally referred to as ªelectronic
An organic polymer that possesses the electrical, electronic, polymersº and have become of very great scientific and
magnetic, and optical properties of a metal while retaining the technological importance since 1990 because of their use in
mechanical properties, processibility, etc. commonly associ- light emitting diodes.[1] The emeraldine base form of polyani-
ated with a conventional polymer, is termed an ªintrinsically line and trans-(CH)x are shown in Figure 1 to illustrate the
conducting polymerº (ICP) more commonly known as a increases in electrical conductivity of many orders of magni-
ªsynthetic metalº. Its properties are intrinsic to a ªdopedº
form of the polymer. This class of polymer is completely
different from ªconducting polymersº which are merely a
physical mixture of a nonconductive polymer with a conduct-
ing material such as a metal or carbon powder distributed
throughout the material.

The Concept of Doping

Conjugated organic polymers are either electrical insula-

tors or semiconductors. Those that can have their conductivity
[*] Prof. A. G. MacDiarmid
Department of Chemistry
University of Pennsylvania
Philadelphia, PA 19104-6323 (USA)
Fax: (‡ 1) 215-898-8378
E-mail: macdiarm@sas.upenn.edu
[**] Copyright The Nobel Foundation 2001. We thank the Nobel Figure 1. Conductivity of electronic polymers. Conductivity increases with
Foundation, Stockholm, for permission to print this lecture. increased doping.

Angew. Chem. Int. Ed. 2001, 40, 2581 ± 2590  WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001 1433-7851/01/4014-2581 $ 17.50+.50/0 2581
REVIEWS A. G. MacDiarmid

tude which can be obtained by doping. The conductivity
attainable by an electronic polymer has very recently been
increased an infinite number of times by the discovery of
superconductivity in regioregular poly(3-hexylthiophene).[2]
Although this phenomenon was present only in a very thin
layer of the polymer in a Field Effect (FET) configuration at a
very low temperature (ca. 2 K) it represents an historical
quantum leapÐsuperconductivity in an organic polymer!
Prior to the discovery of the novel protonic acid doping of
polyaniline, during which the number of electrons associated
with the polymer chain remain unchanged,[3] the doping of all
conducting polymers had previously been accomplished by
redox doping. This involves the partial addition (reduction) or
removal (oxidation) of electrons to or from the p system of
the polymer backbone.[4±6]
The concept of doping is the unique, central, underlying,
and unifying theme which distinguishes conducting polymers
from all other types of polymers.[7] During the doping process,
an organic polymer, either an insulator or semiconductor
having a small conductivity, typically in the range 10ÿ10 to
10ÿ5 S cmÿ1, is converted into a polymer which is in the
ªmetallicº conducting regime (ca. 1 to 104 S cmÿ1). The
controlled addition of known, usually small ( 10 %) non-
stoichiometric quantities of chemical species results in
dramatic changes in the electronic, electrical, magnetic,
optical, and structural properties of the polymer. Doping is
reversible to produce the original polymer with little or no
degradation of the polymer backbone. Both doping and
undoping processes, involving dopant counterions which
stabilize the doped state, may be carried out chemically or
electrochemically.[6] Transitory doping by methods which
introduce no dopant ions are also known.[8]
By controllably adjusting the doping level, a conductivity
anywhere between that of the non-doped (insulating or
semiconducting) and that of the fully doped (highly conduct-
ing) form of the polymer can be easily obtained. Conducting
blends of a (doped) conducting polymer with a conventional
polymer (insulator), whose conductivity can be adjusted by
varying the relative proportions of each polymer, can be
made.[9] This permits the optimization of the best properties of
each type of polymer.
Since the initial discovery in 1977, that polyacetylene
(CH)x , now commonly known as the prototype conducting
polymer, could be p- or n-doped either chemically or electro-
chemically to the metallic state,[7, 10, 11] the development of the
field of conducting polymers has continued to accelerate at an
unexpectedly rapid rate and a variety of other conducting
polymers and their derivatives have been discovered.[5, 6] This
rapid growth rate has been stimulated by the fields funda-
mental synthetic novelty and importance to a cross-discipli-
nary section of investigatorsÐchemists, electrochemists,
biochemists, experimental and theoretical physicists, and
electronic and electrical engineersÐand to important tech-
nological emerging applications of these materials.
In the ªdopedº state, the backbone of a conducting polymer
consists of a delocalized p system. In the undoped state, the
polymer may have a conjugated backbone such as in trans-
(CH)x which is retained in a modified form after doping, or it
may have a nonconjugated backbone, as in polyaniline
(leucoemeraldine base form), which becomes truly conjugat-
ed only after p-doping, or a nonconjugated structure as in the
emeraldine base form of polyaniline which becomes con-
jugated only after protonic acid doping.
Redox Doping
All conducting polymers (and most of their derivatives), for
example, poly-(para-phenylene) (1), poly(phenylenevinyl-
ene) (2), polypyrrole (3), polythiophene (4), polyfuran (5),
poly(heteroaromatic vinylenes) (6; where Y ˆ NH, NR, S, O);
polyaniline (7), etc., undergo either p- and/or n-redox doping

Alan MacDiarmid was born in New Zealand 74 years ago and after obtaining his higher education at the University of New
Zealand (M.Sc. 1950), University of Wisconsin (Ph.D. 1953), and Cambridge University (Ph.D. 1955), he joined the faculty
of the University of Pennsylvania in 1955, where he is currently Blanchard Professor of
Chemistry. During the past 24 years he has been involved exclusively with conducting polymers,
particularly the synthesis, chemistry, doping, electrochemistry, conductivity, magnetic and optical
properties, and processing of polyacetylene and polyaniline. He is the author/co-author of
approximately 600 research papers and 20 patents. He is the recipient of numerous awards and
honorary degrees both nationally and internationally. In 1973, he began research on (SN)x, an
unusual polymeric material with metallic conductivity. His interest in organic conducting
polymers began in 1975 when he was introduced to a new form of polyacetylene by Dr. Hideki
Shirakawa at the Tokyo Institute of Technology. The ensuing collaboration between
MacDiarmid, Shirakawa, and Alan Heeger (then at the Department of Physics at the University
of Pennsylvania) led to the historic discovery of metallic conductivity in an organic polymer, and
the award of the Nobel Prize for Chemisty, 2000.

2582 Angew. Chem. Int. Ed. 2001, 40, 2581 ± 2590

Synthetic Metals
by chemical and/or electrochemical processes during which
the number of electrons associated with the polymer back-
bone changes.[5, 6] Selected examples of the different types of
doping are presented below.
Chemical and Electrochemical p-Doping
p-Doping, that is, partial oxidation of the p backbone of an
organic polymer, was first discovered by treating trans-(CH)x
with an oxidizing agent such as iodine,[7] [Eq. (1)]
trans-(CH)x ‡ 1.5xy I2 ÿ! [CH‡y(I3)yÿ]x (y  0.07) (1)
This process was accompanied by an increase in conduc-
tivity from ca. 10ÿ5 S cmÿ1 to ca. 103 S cmÿ1. If the polymer is
stretch-oriented five- to six-fold before doping, conductivities
parallel to the direction of stretching up to around 105 S cmÿ1
can be obtained.[5, 6]
Approximately 85 % of the positive charge is delocalized
over 15 CH units (depicted in Scheme 1 for simplicity over
only five units) to give a positive soliton.
Scheme 1.
p-Doping can also be accomplished by electrochemical
anodic oxidation by immersing a trans-(CH)x film in, for
example, a solution of LiClO4 dissolved in propylene carbo-
nate and attaching it to the positive terminal of a DC (direct
current) power source, the negative terminal being attached
to an electrode also immersed in the solution,[10] [Eq. (2)].
trans-(CH)x ‡ (xy) (ClO4)ÿ ÿ! [(CH‡y(ClO4)yÿ]x ‡ (xy)eÿ (y  0.1) (2)
Chemical and Electrochemical n-Doping
n-Doping, that is, partial reduction of the backbone
p system of an organic polymer, was also discovered using
trans-(CH)x by treating it with a reducing agent such as liquid
sodium amalgam or preferably sodium naphthaline[7] [Eq. (3)
(Nphth ˆ naphthaline)].
trans-(CH)x ‡ (xy)Na‡(Nphth)ÿ ÿ! [Nay‡(CH)ÿy]x ‡ Nphth (y  0.1) (3)
The antibonding p system is partially populated by this
process which is accompanied by an increase in conductivity
of about 103 S cmÿ1.
n-Doping can also be carried out by electrochemical
cathodic reduction[11] by immersing a trans-(CH)x film in, for
example, a solution of LiClO, dissolved in tetrahydrofuran
and attaching it to the negative terminal of a DC power
Angew. Chem. Int. Ed. 2001, 40, 2581 ± 2590
REVIEWS
source, the positive terminal being attached to an electrode
also immersed in the solution [Eq. (4)].
trans-(CH)x ‡ (xy)Li‡ ‡ (xy)eÿ ÿ! [Liy‡(CH)ÿy]x (y  0.1) (4)
In all chemical and electrochemical p- and n-doping
processes discovered for (CH)x and for the analogous
processes in other conducting polymers, counter ªdopantº
ions are introduced which stabilize the charge on the polymer
backbone. In each case, spectroscopic signatures, for example,
those of solitons, polarons, bipolarons, etc., are obtained
characteristic of the given charged polymer. However, the
doping phenomena concept extends considerably beyond that
given above to ªdopingº processes where no counter dopant
ion is involved, that is, to doping processes in which transitory
ªdopedº species are produced, which have similar spectro-
scopic signatures to polymers containing dopant ions. This
type of doping can provide information not obtainable by
chemical or electrochemical doping. Examples of such types
of redox doping which can be termed ªphoto-dopingº and
ªcharge-injection dopingº are given below.
Doping Involving no Dopant Ions
Photo-Doping
When trans-(CH)x for example, is exposed to radiation of
energy greater than its band gap, electrons are promoted
across the gap and the polymer undergoes ªphoto-dopingº.
Under appropriate experimental conditions, spectroscopic
signatures characteristic of, for example, solitons can be
observed[12] (Scheme 2). The positive and negative solitons
Scheme 2.
are here illustrated diagrammatically for simplicity as residing
only on one CH unit; they are actually delocalized over ca.
15 CH units. They disappear rapidly because of the recombi-
nation of electrons and holes when irradiation is discontinued.
If a potential is applied during irradiation, then the electrons
and holes separate and photoconductivity is observed.
Charge-Injection Doping
Charge-injection doping is most conveniently carried out
using a metal/insulator/semiconductor (MIS) configuration
involving a metal and a conducting polymer separated by a
thin layer of a high dielectric strength insulator. It was this
approach, which resulted in the observance of superconduc-
tivity in a polythiophene derivative, as described previously.
Application of an appropriate potential across the structure
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can give rise, for example, to a surface charge layer, the
ªaccumulationº layer which has been extensively investigated
for conducting polymers.[8, 13] The resulting charges in the
polymer, for example, (CH)x or poly(3-hexylthiophene), are
present without any associated dopant ion. The spectroscopic
properties of the charged species so formed can therefore be
examined in the absence of dopant ion. Using this approach,
spectroscopic studies of (CH)x show the signatures character-
istic of solitons and the mid-gap absorption band observed in
the chemically and electrochemically doped polymer. How-
ever, coulombic interaction between charge on the chain and
dopant ion is a very strong interaction and one that can totally
alter the energetics of the system.
Non-Redox Doping
This type of doping differs from redox doping described
above in that the number of electrons associated with the
polymer backbone does not change during the doping process.
The energy levels are rearranged during doping. The emer-
aldine base form of polyaniline was the first example of the
doping of an organic polymer to a highly conducting regime
by a process of this type to produce an environmentally stable
polysemiquinone radical cation. This was accomplished by
treating emeraldine base with aqueous protonic acids
(Scheme 3) and is accompanied by a nine to ten order of
magnitude increase in conductivity (up to around 3 S cmÿ1) to
produce the protonated emeraldine base.[14±16] Protonic acid
doping has subsequently been extended to systems such as
poly(heteroaromatic vinylenes).[17]
Scheme 3.
The Polyanilines
The polyanilines refer to a very important class of
electronic/conducting polymers. They can be considered as
being derived from a polymer, the base form of which has the
generalized composition given in Scheme 4 a, and which
consists of alternating reduced, and oxidized, repeat units
(Scheme 4 a).[3, 14, 15] The average oxidation state can be varied
continuously from y ˆ 1 to give the completely reduced
polymer, to y ˆ 0.5 to give the ªhalf-oxidizedº polymer, to
y ˆ 0 to give the completely oxidized polymer (Scheme 4 b ±
d). The terms ªleucoemeraldineº, ªemeraldineº, and ªperni-
granilineº refer to the different oxidation states of the
polymer where y ˆ 1, 0.5, and 0, respectively, either in the
base form, for example, emeraldine base, or in the protonated
salt form, for example, emeraldine hydrochloride.[3, 14, 15] In
principle, the imine nitrogen atoms can be protonated in
2584
A. G. MacDiarmid
Scheme 4. a) Generalized composition of polyanilines indicating the
reduced and oxidized repeat units, b) completely reduced polymer,
c) half-oxidized polymer, d) fully oxidized polymer.
whole or in part to give the corresponding salts, the degree of
protonation of the polymeric base depending on its oxidation
state and on the pH of the aqueous acid. Complete
protonation of the imine nitrogen atoms in emeraldine base
by aqueous HCl, for example, results in the formation of a
delocalized polysemiquinone radical cation[3, 15, 18] and is
accompanied by an increase in conductivity of about 1010.
The partly protonated emeraldine hydrochloride salt can be
synthesized easily either by the chemical or electrochemical
oxidative polymerization of aniline.[3, 14, 15] It can be deproto-
nated by aqueous ammonium hydroxide to give emeraldine
base powder (a semiconductor).
Allowed Oxidation States
As can be seen from the generalized formula of polyaniline
base (Scheme 4 a), the polymer could, in principle, exist in a
continuum of oxidation states ranging from the completely
reduced material in the leucoemeraldine oxidation state, y ˆ 1
to the completely oxidized material in the pernigraniline
oxidation state, y ˆ 0. However, we have shown[16] that at least
in N-methyl-2-pyrrolidinone (NMP) solution in the range
y ˆ 1 to y ˆ 0.5 (emeraldine oxidation state) only two
chromophores are present, characteristic of y ˆ 1, and y ˆ
0.5 species and that all intermediate oxidation states consist,
at the molecular level, only of mixtures of the chromophores
characteristic of these two states.
Since most of the properties of polyaniline of interest are
concerned with the solid state, we have carried out a series of
studies in the solid state which show that the same phenom-
enon is true in the y ˆ 1 to y ˆ 0.5 oxidation-state range and in
the y ˆ 0.5 to y ˆ 0 oxidation-state range. Within each of these
ranges all intermediate oxidation states consist, at the
Angew. Chem. Int. Ed. 2001, 40, 2581 ± 2590
Synthetic Metals
molecular level, only of mixtures of the chromophores
characteristic of the two states defining the beginning and
end of each range.[19, 20]
Doping
Polyaniline holds a special position amongst conducting
polymers in that its most highly conducting doped form can be
reached by two completely different processesÐprotonic acid
doping and oxidative doping. Protonic acid doping of
emeraldine base units with, for example 1m aqueous HCl
results in complete protonation of the imime nitrogen atoms
to give the fully protonated emeraldine hydrochloride
salt.[14, 15]
As shown in Figure 2, protonation is accompanied by a 9 to
10 order of magnitude increase in conductivity reaching
saturation in ca. 1m aqueous HCl.
Figure 2. Conductivity of emeraldine base as a function of the pH of the
HCl dopant solution as it undergoes protonic acid doping (* and &
represent two independent series of experiments).[14, 15]
The same doped polymer can be obtained by chemical
oxidation (p-doping) of leucoemeraldine base.[3] This actually
involves the oxidation of the s/p system rather than just the
p system of the polymer as is usually the case in p-type doping.
Its reaction with a solution of chlorine in carbon tetrachloride
proceeds to give emeraldine hydrochloride (Scheme 5).
Scheme 5.
Nanoelectronics
The basic purpose of this research is to blend the now well-
established field of electronic/conducting polymers with the
new, emerging field of nanoscience, by electrostatic fabrica-
tion (ªelectrospinningº) to produce ªnanoelectronicsºÐelec-
Angew. Chem. Int. Ed. 2001, 40, 2581 ± 2590
REVIEWS
tronic junctions and devices significantly smaller than the
diameter of a human hair (ca. 50 000 nm). It is commonly
accepted that a nanomaterial is defined as one consisting of a
substance or structure which exhibits at least one dimension
of less than 100 nm (0.1 mm).[21]
Our objectives were: 1) to develop a method by which
nanofibers (diameter < 100 nm) of organic polymers could be
controllably and reproducibly fabricated such that in one
given preparation, all fibers would have a diameter < 100 nm
and 2) to reproducibly and controllably fabricate, for the first
time, nanofibers of electronic polymers (in their semiconduct-
ing and metallic regimes) and/or their blends in conventional
organic polymers for the purpose of ascertaining their
applicability in the fabrication of nanoelectronic devices.
We have made substantial progress in achieving these
objectives by using a relatively little known, simple, conven-
ient, and inexpensive ªelectrospinningº method.[22±27] We have
previously reported[23] fabrication of the first conducting
polymer fibers (diameter  950 nm to 2100 nm) of polyaniline
doped with rac-camphorsulfonic acid (PAn ´ HCSA) as a
blend in poly(ethylene oxide) (PEO). We were surprised to
find that an electronic polymer, such as polyaniline, which
might have been expected to be more susceptible to
degradation than most conventional organic polymers, sur-
vived, without observable chemical or physical change,
following the 25 000 V electrospinning fabrication process in
air at room temperature.
Electrospinning
The electrospinning technique involves a simple, rapid,
inexpensive, electrostatic, nonmechanical method in which a
polymer solution in a variety of different possible common
solvents, including water, is placed in a hypodermic syringe or
in a glass pipette, at a fixed distance (5 ± 30 cm) from a metal
cathode.[24] The positive (anode) terminal of a variable high
voltage transformer is attached to the metal tip of the
hypodermic syringe or to a wire inserted into the polymer
solution in the glass pipette, the negative terminal being
attached to the metal cathode. The tip of the syringe can be
placed vertically over the cathode or at any other convenient
angle to it. When the voltage applied between the anode and
cathode reaches a critical value, ca. 14 000 V at a ca. 20 cm
separation, the charge overcomes the surface tension of the
deformed drop of the polymer solution on the tip of the
syringe and a jet is produced. Since the polymer molecules all
bear the same (positive) charge, they repel each other while
traveling in air during a few milliseconds from the anode to
cathode and become separated.[25] At the same time, evapo-
ration of the solvent molecules occurs rapidly. Evaporation of
solvent is also enhanced because the similarly charged
(positive) solvent molecules repel each other. Under appro-
priate conditions, dry, meters-long fibers accumulate on the
surface of the cathode resulting in a nonwoven mesh of nano-
to micron-diameter fibers depending on experimental param-
eters (Figure 3).
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REVIEWS
Figure 3. 50 wt % Nanofiber blend of PAn ´ HCSA fabricated from 2 wt %
PAn ´ HCSA and 2 wt % PEO from chloroform solution at 25 000 V (anode/
cathode separation, 25 cm). Scale bar: 100 000 nm.
Nanofiber Fabrication
Since the submicron fibers (500 ± 1600 nm) obtained in our
initial work[23] were not classifiable as true ªnanofibersº, our
immediate objective was to break the ªnanotechnology
barrierº and to consistently and reproducibly fabricate true
nanofibers (diameter < 100 nm) of an organic polymer. This
was accomplished (see Figure 4) using an 8 wt % solution of
Figure 4. Electrospun fibers of polystyrene (see text). Scale bar: 1000 nm.
The extended length of the fibers is clearly visible.
polystyrene (Mw 212 400) in tetrahydrofuran at a potential of
20 000 V between the anode and cathode which were sepa-
rated by 30 cm. The fibers were collected as a mat on an
aluminum target and were found to have diameter character-
istics: average: 43.1 nm, maximum: 55.0 nm, minimum:
26.9 nm. Other studies involving polystyrene gave fibers
whose diameters were consistently < 100 nm; average:
30.5 nm (maximum: 44.8 nm, minimum: 16.0 nm). It might
also be noted that the 16 nm fiber is only around 30
polystyrene molecules wide. It is also of interest to note that
a 16 nm fiber, such as the one mentioned above, lies well
within the ca. 4 ± 30 nm diameter range of multiwalled carbon
nanotubes.[26]
Electronic Polymer Fibers
By using a previously applied method for producing
polyaniline fibers[27] we have prepared highly conducting
sulfuric acid doped polyaniline fibers (diameters, average:
139 nm, maximum: 275 nm, minimum: 96 nm) by placing a ca.
20 wt % solution of polyaniline in 98 % sulfuric acid in a glass
2586
A. G. MacDiarmid
pipette with the tip ca. 3 cm above the surface of a copper
cathode immersed in pure water at 5000 V potential differ-
ence. The fibers collect in or on the surface of the water. The
conductivity of a single fiber was ca. 0.1 S cmÿ1, as expected
since partial fiber de-doping occurred in the water cathode.
The diameter and length of the fibers appear (Figure 5) to be
sensitive to the nature of the polyaniline used. No great
difficulty is foreseen in producing fibers < 100 nm diameter.
Figure 5. 100 % polyaniline fiber with an average diameter of 139 nm.
It is relatively easy to prepare conducting blends of
PAn.HCSA in a variety of different conventional polymers
such as polyethylene oxide, polystyrene, polyacrylonitrile, etc.
For example, ca. 20 wt % blends of PAn ´ HCSA in polystyr-
ene (Mw 114 200) are obtained by electrospinning a chloro-
form solution; fiber diameter characteristics: average:
85.8 nm, maximum: 100.0 nm, minimum: 72.0 nm. These
fibers are sufficiently electrically conductive that their scan-
ning electron micrographs (SEMs) may be recorded without
the necessity of applying a gold coating.
Separate, individual nanofibers can be collected and
examined if so desired. An appropriate substrateÐglass slide,
silicon wafer, or loop of copper wire, etc.Ðis held between the
anode and cathode at a position close to the cathode for a few
seconds to collect individual fibers (see Figure 6).
Figure 6. Polystyrene fibers collected on a bent copper wire (magnification
33  ) and subsequently coated with a thin layer of polypyrrole by in situ
deposition from aqueous solution. Scale bar: 1 mm.
Current/voltage (I/V) curves are given in Figure 7 for a
single 419 nm diameter fiber (Fiber 1) and for a ca. 600 nm
diameter fiber (Fiber 2) of a blend of 50 wt % PAn ´ HCSA
and poly(ethylene oxide) collected on a silicon wafer coated
with a thin layer of SiO2 . Two gold electrodes separated by
60.3 mm are deposited on the fiber after its deposition on the
substrate.
Angew. Chem. Int. Ed. 2001, 40, 2581 ± 2590
Synthetic Metals
Figure 7. Current/voltage curves of 50 wt % PAn ´ HCSA/PEO blend
nanofiber (see text).
Nanofibers as Substrates
The large surface to volume ratio offered by nanofibers
makes them excellent, potentially useful substrates for the
fabrication of coaxial nanofibers consisting of superimposed
layers of different materials. Catalysts and electronically
active materials can be deposited on them by chemical,
electrochemical, solvent, chemical vapor, or other means, for
use in nanoelectronic junctions and devices.
We have found, for example, that polyacrylonitrile nano-
fibers can be easily and evenly coated with a 20 ± 25 nm layer
of conducting polypyrrole (Figure 8) by immersion in an
aqueous solution of polymerizing polypyrrole.[28] Analogous-
ly, we have found that electroless deposition of metals can also
be performed. Polyacrylonitrile fibers, for example, can be
evenly coated with gold by electroless deposition.[29]
Figure 8. Scanning electron micrograph of conducting polypyrrole-coated
polyacrylonitrile nanofibers. Scale bar: 1000 nm.
Carbon Nanofibers
As reported polyacrylonitrile fibers may be thermally
converted into carbon nanofibers with some shrinkage.[30]
We have similarly converted polyacrylonitrile nanofibers into
carbon nanofibers.
In summary, electronic polymers have been used for the
past 20 years to produce rectifying diodes by Schottky and p/n
junctions, transistors, light-emitting devices, photovoltaic
cells, rechargeable batteries, etc.[1] Now, the ability to fab-
Angew. Chem. Int. Ed. 2001, 40, 2581 ± 2590
REVIEWS
ricate nanofibers of electronic polymers which are only a few
molecules thick suggests the emergence of a field of nano-
electronics whereby the electronic properties of such nano-
fibers can be exploited for technological purposes.
Line Patterning of Conducting Polymers[30]
One of the exciting challenges of the first part of this
century will be the development of low-cost disposable
plastic/paper electronic devices.[31±33] Conventional inorganic
conductors, such as metals, and semiconductors, such as
silicon, commonly require multiple etching and lithographic
steps in fabricating them for use in electronic devices. The
number of processing steps and chemical etching steps
involved limit the minimum price and therefore their applic-
ability in disposable electronics. On the other hand, conduct-
ing polymers combine many advantages of plastics, for
example, flexibility and processing from solution, with the
additional advantage of conductivity either in the metallic or
semiconducting regimes; however, the lack of simple methods
to obtain inexpensive conductive polymer shapes/patterns
limit many applications. We here describe a novel, simple, and
cheap method to prepare patterns of conducting polymers by
a process which we term, ªLine Patterningº.
Line Patterning uses the difference in selected physical and/
or chemical properties between a substrate and insulating
lines which have been printed on it by a conventional copying
or printing process towards a fluid (or vapor) to which they
are both simultaneously exposed. The substrate and printed
lines react differently or at different rates with the fluid (or
vapor) to which they have been exposed. This results in a non-
uniform deposition on the substrate as compared to the
printed lines. If the fluid contains a conducting polymer, which
remains as a film after evaporation of the solvent, a pattern of
conducting polymer results. A pattern is first designed on a
computer and is then printed on, for example, an overhead
transparency using a standard, non-modified office laser
printer.
The printed (insulating) lines can be easily removed, if
necessary, in a few seconds by ultrasonic treatment in toluene,
dissolving the printed lines and leaving a clean pattern of
deposited material on the substrate whose shape was origi-
nally defined by the now nonexistent printed lines. Line
Patterning has the following advantages: no photolithography
is involved; no printing of conducting polymer is involved; it
uses only, for example, a standard office laser printer, which is
not modified in any way; commercially available flexible,
transparent plastic or paper substrates can be used; solutions
of commercially available conducting or nonconducting
polymers can be used from which the polymers may be
deposited on substrates, it is inexpensive; rapid development
of customized patterns (within hours) from a computer
designed pattern to product is routine.
We have exploited, for example, the observation that a
commercial dispersion of poly-3,4-ethylenedioxythiophene
(PEDOT, ªBaytron Pº, Bayer Corp.) wets commercial plastic
overhead transparency, but not the lines printed on it by a
standard office laser printer. A coating of PEDOT can be
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applied by a roller and after evaporation of the solvent; the
printed lines can be easily and cleanly removed by sonication,
leaving only the conducting polymer on the transparency.
Two electrodes were prepared in this way, each containing
25 lines inchÿ1. A drop of a standard commercial polymer
dispersed liquid crystal (PDLC) display[34] mixture containing
an optical adhesive and 15 mm spacer spheres was placed on
the center of each electrode. The second electrode was placed
on top at an angle of 908 to the first. This resulted in a (25 
25), that is, 625 pixels (square-inch matrix)ÿ1 (Figure 9).
Exposure to UV light for a few minutes resulted in polymer-
ization of the mixture to bind the two electrodes together and
to produce a free-standing working PDLC display device.
When an electrode pattern of 100 lines inchÿ1 was used a
working 10 000 pixel square-inchÿ1 display was produced.
Figure 9. Fabrication of a 625 pixel PDLC display (see text).
We have devised a novel way of separating conducting
polymer circuits from each other by making use of the height
(ca. 4 ± 5 mm) of the printed toner lines, made by using a
standard office printer, above the substrate, for example, on
an overhead transparency. This is illustrated (Figures 10 and
11) by a ªpush buttonº switch to open and close a simple
electrical circuit. A combination of two patterned trans-
parencies where the two adjacent conductive areas are
electrically separated from each other by two ca. 4 ± 5 mm
Figure 10. A simple electronic circuit (ªpush buttonº switch).
Figure 11. ªPush buttonº switch.
2588
A. G. MacDiarmid
nonconductive printed toner lines is obtained by placing the
printed lines on top of each other as shown in Figures 11 and
12. Depression of the areas labeled ªPRESSº causes the
upper transparency to bend. This electrically connects the
conducting PEDOT surfaces. When released, the transpar-
ency film returns back to its original position, thus breaking
the electrical circuit.
The two-dimensional conducting polymer circuits may be
readily converted into three-dimensional circuits by two
different methods as shown in Figure 12 simply by 1) stapling
two two-dimensional circuits together using a common office
stapler. The metal staple joins together electrically the
conducting polymer areas on two different substrates or
2) making a pinhole through the sheets, as shown, before
applying the PEDOT solution. Some of the solution enters the
pinhole and joins together electrically the conducting surfaces
on the two different circuits.
Figure 12. Three-dimensional connections; a) connected with staple,
b) connected by a coated hole; * ˆ connection to power supply.
We have recently observed a curious field effect which thin
films of PEDOT exhibit when exposed to a positive gate
potential in an FET configuration as shown in Figure 13. A
source/drain electrode and a gate electrode are prepared by
Line Patterning and are covered by a thin layer of PEDOT as
described above. A drop of the optical adhesive containing
spacer spheres described above is placed on the source/drain
Figure 13. Field-effect doped ªPEDOTº. a) FET-type device, b) field-
effect configuration.
Angew. Chem. Int. Ed. 2001, 40, 2581 ± 2590
Synthetic Metals
electrode upon which the gate electrode is then placed at 908.
The two electrodes are manually squeezed together and the
optical adhesive is polymerized by exposure to UV light as
was done for the PDLC display described above. Several
thousand of these interconnected transistor-type devices
could be readily fabricated per square inch by the Line
Patterning process, if it were considered desirable. The free-
standing, flexible device shown in Figures 13 and 14 is
produced.
Figure 14. FET-type device.
The device exhibits the same general reversible features
commonly associated with a field effect transistor (FET) as
shown in Figure 15. The doped ªmetallicº PEDOT film (s 
2 S cmÿ1 at room temperature) would not be expected to show
a change in conductivity by exposure to a field of this type
Figure 15. Field effect transistor characteristics. I ˆ source ± drain current;
U ˆ gate voltage.
under the configuration used. We believe this effect presents
an entirely new method for ascertaining the nature of highly
doped ªmetallicº conducting polymers. It has frequently been
postulated that a doped conducting polymer consists of
metallic ªislandsº surrounded by lowly conducting ªbeachesº
as shown in Figure 16. We postulate that in the effect we have
observed only the lowly conducting ªbeachesº and not the
metallic ªislandsº respond to the applied field. The applica-
tion of an electric field changes the conductivity of the
Angew. Chem. Int. Ed. 2001, 40, 2581 ± 2590
REVIEWS
Figure 16. Percolation field effect in doped conducting polymers. Metallic
ªislandsº separated by ªbeachesº of non- or lowly conducting (semi-
conducting) polymer. The field changes the conductivity of the semi-
conducting ªbeachesº but not that of the metallic ªislandsºÐhence the
field changes the extent of electrical percolation between the metallic
ªislandsºÐand therefore changes the bulk conductivity of the material.
ªbeachesº and hence the extent of electrical percolation in the
source/drain PEDOT electrode between the metallic ªis-
landsº, hence changing the bulk conductivity of the material.
The response time for our device is much slower than for a
conventional field effect transistor. We therefore conjecture
that the chief changes in conductivity are probably caused by
slow diffusion of the dopant anions under influence of the
applied field. On removal of the field the system reverts to its
original state.
Preliminary studies show that the effect is also present in
polyaniline; it may therefore possibly be found in many other
conducting polymers and would thus represent a general
phenomenon characteristic of all conducting polymers, at
least within certain ranges of doping.
Summary
* Polyacetylene, (CH)x, the simplest organic polymer, can be
reversibly doped to the metallic regime by partial oxidation
or reduction either chemically or electrochemically.
* Polyaniline can be doped to the metallic regime by a simple
acid/base protonation.
* A large number of electronic conductive polymers are now
known.
* A variety of technological applications of electronic con-
ductive polymers, present and projected, are apparent.
This Nobel Prize has world-wide implications since it shows
the ever-increasing importance of interdisciplinary researchÐ
in this case collaborative research between a polymer chemist,
Hideki Shirakawa,[35] Alan Heeger,[36] a physicist, and myself,
an organometallic chemist. Each of us had the task of learning
the specialized scientific language of the other in order to
collectively focus on one specific scientific challenge, an
example of where 1 ‡ 1 ‡ 1 is more than 3!
The prize is also recognition of the good fortune that Alan,
Hideki, and I had in having each other as such excellent
colleagues and also in having such creative colleagues in each
of our respective individual research groupsÐthe work stem-
ming from a research group cannot be better than the persons
carrying it out. The prize is a recognition of them and their
work and also the work of countless others world-wide during
the past 23 years who put the ªflesh on the skeleton workº
carried out by us in the 1970s at Penn (University of
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Pennsylvania). If it were not for them there would be no prize
today in the field.
Research in an experimental science (and also in many other
fields) cannot be accomplished without financial support for
stipends, apparatus, supplies and the like. A funding organ-
ization and project officers within such an organization have
tremendous control over the future of science and technology in
any given country. In this respect Dr. Kenneth J. Wynne, my
contracting officer at the US Office of Naval Research for
many years, before his recent retirement, had the scientific
intuition and foresight to fund our first work on conducting
polymersÐthe first funding of work of this type anywhere in
the world. He funded it because of its scientific interest. The fact
that it now has great technological potential was not a
consideration at that time.
ªOf what use is a beautiful poemº? It gives intellectual
stimulation and enjoyment. Similarly with research. If it has
some practical use, that is merely ªicing on the cake!º
Early studies: Polyacetylene, (CH)x : Alan J. Heeger[36]
(formerly, Physics Department, University of Pennsylvania),
Hideki Shirakawa[35] (Tsukuba University), and many under-
graduate, graduate students, and post doctoral fellows. Finan-
cial support: Principally, US Office of Naval Research (Dr.
K. J. Wynne, Program Manager); University of Pennsylvania
Materials Science Laboratory.
Polyaniline: Arthur J. Epstein (Physics Dept., Ohio State
University) and many undergraduate, graduate students, and
post doctoral fellows. Financial support: Principally, US Office
of Naval Research (Dr. K. J. Wynne, Program Manager);
University of Pennsylvania Materials Science Laboratory.
Recent Studies: Nanofibers (ªElectrospinningº): I. D. Nor-
ris, J. Gao, F. K. Ko, W. E. Jones, Jr., A. T. Johnson, Jr.
Financial support: US Office of Naval Research (Dr. K. J.
Wynne, Program Manager); Army Research OfficeÐMURI.
Line Patterning: D. Hohnholz, H. Okuzaki. Financial
support: Subcontract, Kent Displays, Inc. (ONR-SBIR Pro-
gram); US Office of Naval Research (Dr. K. J. Wynne,
Program Manager); Fellowship from Ministry of Education,
Science, Culture and Sports, Japan.
Received: May 2, 2001 [A 470]
[1] Handbook of Organic Conductive Materials and Polymers (Ed.: H. S.
Nalwa), Wiley, New York, 1997; Handbook of Conducting Polymers
(Eds.: T. A. Skotheim, R. L. Elsenbaumer, J. F. Reynolds), 2nd ed.,
Marcel Dekker, New York, 1998.
[2] J. H. Schon, A. Dodabalapur, Z. Bao, C. Kloc, O. Schenker, B.
Batlogg, Nature 2001, 410, 189.
[3] A. G. MacDiarmid, A. J. Epstein, Faraday Discuss. Chem. Soc. 1989,
88, 317, and refs therein.
[4] A. G. MacDiarmid, A. J. Heeger, Synth. Met. 1979/80, 1, 101, and refs
therein.
[5] Handbook of Conducting Polymers, Vol 1&2 (Ed.: T. A. Skotheim),
Marcel Dekker, New York, 1986.
[6] M. G. Kanatzidis, Chem. Eng. News 1990, 68(49), 36.
[7] C. K. Chiang, C. R. Fincher, Jr., Y. W. Park, A. J. Heeger, H.
Shirakawa, E. J. Louis, A. G. MacDiarmid, Phys. Rev. Lett. 1977, 39,
2590
A. G. MacDiarmid
1098; C. K. Chiang, M. A. Druy, S. C. Gau, A. J. Heeger, E. J. Louis,
A. G. MacDiarmid, J. Am. Chem. Soc. 1978, 100, 1013.
[8] K. E. Ziemelis, A. T. Hussain, D. D. C. Bradley, R. H. Friend, J. Rilhe,
G. Wegner, Phys. Rev. Lett. 1991, 66, 2231.
[9] V. G. Kulkarni, W. R. Mathew, J. C. Campbell, C. J. Dinkins, P. J.
Durbin, 49th ANTEC Conference Proceedings (Montreal, Canada 5 ±
9 May), Society of Plastic Engineers and Plastic Engineering, 1991,
p. 663; L. W. Shacklette, N. F. Colaneri, V. G. Kulkarni, B. Wessling, in
49th ANTEC Conference Proceedings (Montreal, Canada, 5 ± 9 May),
Society of Plastic Engineers and Plastic Engineering, 1991, p. 665.
[10] P. J. Nigrey, A. G. MacDiarmid, A. J. Heeger, J. Chem. Soc. Chem.
Commun. 1979, 594.
[11] D. MacInnes, Jr., M. A. Druy, P. J. Nigrey, D. P. Nairns, A. G.
MacDiarmid, A. J. Heeger, J. Chem. Soc. Chem. Commun. 1981, 317.
[12] A. J. Heeger, S. Kivelson, J. R. Schrieffer, W.-P. Su, Rev. Mod. Phys.
1988, 60, 781, and refs therein.
[13] J. H. Burroughes, C. A. Jones, R. H. Friend, Nature 1988, 335, 137;
J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K.
Mackay, R. H. Friend, P. L. Burns, A. B. Holmes, Nature 1990, 347,
539.
[14] J. C. Chiang, A. G. MacDiarmid, Synth. Met. 1986, 13, 193.
[15] A. G. MacDiarmid, J.-C. Chiang, A. F. Richter, A. J. Epstein, Synth.
Met. 1987, 18, 285.
[16] A. G. MacDiarmid, A. J. Epstein, Faraday Discuss. Chem. Soc. 1989,
88, 317, and refs therein; A. G. MacDiarmid, A. J. Epstein in Science
and Applications of Conducting Polymers (Eds.: W. R. Salaneck, D. T.
Clark, E. J. Samuelsen), Adam Hilger, Bristol, 1990, p. 117.
[17] C. C. Han, R. L. Elsenbaumer, Synth. Met. 1989, 30, 123.
[18] A. G. MacDiarmid, J.-C. Chiang, A. F. Richter, N. L. D. Somasiri, A. J.
Epstein in Conducting Polymers (Ed.: L. AlcaceÂr), Reidel, Dordrecht,
1987, p. 105.
[19] F. L. Lu, F. Wudl, M. Nowak, A. J. Heeger, J. Am. Chem. Soc. 1986,
108, 8311.
[20] Y. Sun, A. G. MacDiarmid, A. J. Epstein, J. Chem. Soc. Chem.
Commun. 1990, 529.
[21] ªNanotechnology: A Revolution in the MakingÐVision for R&D in
the Next Decadeº: Report of the Interagency Working Group on
Nanoscience, Engineering, and Technology, March 10, 1999.
[22] A. Formhals, US-A 1 975 504, 1934.
[23] I. D. Norris, M. M. Shaker, F. K. Ko, A. G. MacDiarmid, Synth. Met.
2000, 114, 109; A. G. MacDiarmid, W. E. Jones, Jr., I. D. Norris, J.
Gao, A. T. Johnson, Jr., N. J. Pinto, J. Hone, B. Han, F. K. Ko, H.
Okuzaki, M. Llagune, Synth. Met. 2001, 119, 27.
[24] J. Doshi, D. H. Reneker, J. Electrost. 1995, 35, 151; P. W. Gibson, H. L.
Schreuder-Gibson, D. Riven, AIChE J. 1999, 45, 190.
[25] D. H. Reneker, A. L. Yarin, H. Fong, S. Koombhongse, J. Appl. Phys.
2000, 87, 4531.
[26] S. Iijima, Nature 1991, 354, 56.
[27] D. H. Reneker, I. Chun, Nanotechnology 1996, 7, 216.
[28] Z. Huang, P.-C. Wang, A. G. MacDiarmid, Y. Xia, G. M. Whitesides,
Langmuir 1997, 13, 6480; R. V. Gregory, W. C. Kimbrell, H. H. Kuhn,
Synth. Met. 1989, 28, C823.
[29] A. M. Sullivan, P. A. Kohl, J. Electrochem. Soc. 1995, 142, 2250.
[30] I. Chun, D. H. Reneker, H. Fong, X. Fang, J. Deitzel, N. B. Tan, K.
Kearns, J. Adv. Mater. 1999, 31, 36; D. Hohnholz, A. G. MacDiarmid,
Synth. Met. 2001, 121, 1327.
[31] A. Dodabalapur, Z. Bao, A. Makhija, J. G. Laquindanum, V. R. Raju,
Y. Feng, H. E. Katz, J. Rogers, Appl. Phys. Lett. 1998, 73, 142, and refs
therein.
[32] C. J. Drury, C. M. J. Mutsaers, C. M. Hart, M. Matters, D. M.
de Leeuw, Appl. Phys. Lett. 1998, 73, 108, and refs therein.
[33] H. Okusaki, Y. Osada, J. Intell. Mater. Syst. Struct. 1993, 4, 50.
[34] ªLicristal E7º (Merck Corp., Germany), ªNOA-65 Optical Adhesiveº
(Norland Products, NH).
[35] H. Shirakawa, Angew. Chem. 2001, 113, 2642; Angew. Chem. Int. Ed.
2001, 40, 2574.
[36] A. J. Heeger, Angew. Chem. 2001, 113, 2660; Angew. Chem. Int. Ed.
2001, 40, 2591.
Angew. Chem. Int. Ed. 2001, 40, 2581 ± 2590